Dibasic ether acid derivatives of vanillic acid



Patented Mar. 3, 1953 UNITED STATES OFFICE DIBA'SICETHER ACID .DERIVATIVE'SJDF ViTN-ILLICAEIU Louiafl. Bock; Shelton, Washi, assignor tosiRayonier Incorporated, Sheltoin, Wash, ar -corporation of, Delaware No Drawing.

Application-November 28; 1950,

Serial No. 198;047

in which R is a divalent aliphatic group represented by the following examples:

In accordance with the method of the invention, these acids are all prepared .from vanillic acidby the following series-of reactions:

znoOcon xxx me on Vanillic Acid' C H: O

OOHa NaOC- H OaM aNWNa OUH'zi 01130 ti R. in the above formulas is the samelae described above. Xis chlorine or bromine.

Vanillic acid, the starting material is potentially available in great abundance by the alkaline oxidation of sulfite waste liquor which is a by-product in the manufacture of cellulose from wood. Thus, the products produced by the method of this invention may be made in quantity from raw materials which have, at present, no economic value and are, in fact, a menace to aquatic and marine life as they are usually dumped into rivers or bays.

The preparation of the dibasic acids according to the method of this invention is illustrated by the following examples:

Example 1 A mixture of 84 parts of vanillic acid, 40 parts of sodium hydroxide, 500 parts of water, and 47 parts of ethylene dibromide was placed in a vessel equipped with a mechanical stirrer and reflux condenser. The mixture was stirred at a "opened and thesolution-was saturated with sulfur 2 temperature 1cf 73-7.5 C; for 22. hours. 'l-itrae tion of a sample or the:reaction.mixture-atthis time indicated that 92% of the sodium hydroxide had reacted. Ten parts ofsodium hydroxide was t dded and; stirringaand refluxing was continuedcfor 4- hoursxin order toesaponif-y anytester which mightzhaviectormed. The 'so'lutionlwas then cooled and saturated with: S92. A white precipitate stormed? whichxwas filtered, washed 0 with "water, sandidriedl, The yield was 6358:partszccr- .responding "to-!% ofithe theoreticalHy-ieldl The product imeltedwat aver-230 C; It was further purified byboiiing with 159011 partsof ethyl alcohol and filteringlhotlto:remove anyunreacted:vanillic acid. This. treatment: yielded '54- partsmof white powder melting :at 25789 281 C; Its neutralizatihina equivalent WQiSMIETB: comparedctoL-a theoretical value of 181 'torua dibasieacid ofa the formula C18H18O8. The product was ethane-1,2-bis-(2- methoxy-4-carboxyphenyl) "ether.

Example 2 stainless steel autoclave with mechanical stirrer was charged with" a mixture-of 42 parts of van-illic acid, '20 parts of sodium hydroxide, 300 parts of water and l 5 parts of ethylene 'dichloride; The autoclave was heated with stirring '2 hours at a temperature of 4 42" C. The maximum pressure-was '53 pounds per square inch ('gaugei. Atter c'ool'ing, the autoclave was dioxide; precipitate formed which was filtered and dried. The product was crude ethane- 132 ibis (2 methoxy 4 carboxyrihenyl) ether. The yield was 362.5 parts or" 8'02"l% of theory;

Example '3 A mixture of 336 parts of vanillic acid, 164 parts of sodium hydroxide, 2000 parts of water and 202 parts of trimethylene dibromide was placed in a vessel equipped with mechanical stirrer and reflux condenser. The mixture was stirred and heated to refluxing for 7.25 hours. The resulting clear solution was poured into an excess of dilute hydrochloric acid whereupon a fine precipitate formed. This was removed from the mother liquor by filtration, was washed with water and dried. The product melted at 210-224 C. and had a neutralization equivalent of 182 compared to a theoretical value of 188 for a dibasic acid of the formula CiaHzoOe. The yield was 329 parts or 87.5% of theory. Recrystallization from the monoethyl ether of ethylene glycol gave a product with a melting point 3 of 242-246 C. The product was propane-1,3- bis-(2-methoxy-4-carboxyphenyl) ether.

Example 4 dichlorobutane. The autoclave was heated with stirring 3 hours at 142170 C. The maximum pressure was 133 pounds per square inch (gauge) After cooling the resulting clear solution was poured into an excess of dilute hydrochloric acid. A fine precipitate formed which was removed by filtration. After washing and drying it weighed 68.9 parts. After crystallization from the monoethyl ether of ethylene glycol the melting point was 236-244 C. The neutralization equivalent was 203 compared to a theoretical Q value of 195 for a dibasic acid of the formula CzoH'zzOs. The product was butane-1,4-bis-(2- l methoxy l-carboxyphenyl) ether.

Example 5 A mixture of 330 parts of vanillic acid, 160

'parts of sodium hydroxide, 2000 parts of water and 143 parts of bis-(Z-chloroethyl) ether was placed in a vessel equipped with a mechanical stirrer and heated to refluxing for 40 hours. The clear reaction mixture was poured into an excess :of dilute hydrochloric acid solution whereupon 5a fine precipitate formed. This was filtered, I washed and dried yielding 200 parts of product melting at 208-2l 7 C. The product'had a neutralization equivalent of 199 compared to a theoretical value of 203 for a dibasic acid of the formula .CH22O9. The product was bis(2-meth- ...'oxyl-carboxyphenoxyethyl) ether.

Example 6' A mixture of 138 parts of vanillic acid, 66 parts of sodium hydroxide, 2000 parts of water and 100 7 parts of hexamethylene dibromide was placed in a vessel equipped with a mechanical stirrer and heated to refluxing with stirring for 23 hours. The reaction mixture was cooled and saturated with S02. A precipitate formed which was It was crystallized from the hexane 1,6-bis(2 methoxy -carboxyphenyl) ether. In all of the examples above, the compounds are named according to the Geneva system of nomenclature and all of them are dibasicacids of the general formula first set forth herein.

I textile fibers.

For the preparation of a linear polyester for extrusion into a textile fiber, the preferred acid is the one in which the R group in the above formula is -CH2CH2- as this acid has the highest melting point and the polyesters made from it have highmelting points. For the preparation of linear polyamides and alkyd resins, the B group can be chosen to give the desired softening point and hardness to the resulting polymer. Thus, larger R groups give more flexible resins while the short R groups give harder resins.

My copending application Serial No. 198,048 filed November 28, 1950, describes and claims linear polyesters obtained by the condensation of a dihydric alcohol with the dibasic compounds. I claim:

The method of producing dibasic acids which comprises heating in aqueous solution, vanillic acid, sodium hydroxide and a compound having the formula XRX at a temperature between about 73 C. and 224 C. for a length of time sufficient toform a, compound having the formula 0 CH3 CHsO (H) I if) NaOCOOR-OOOONa and reacting said last-named compoundwith a non-oxidizing mineral acid to' form a dibasic acid having the formula where in allof said formulae R. is a member of the group consisting of --(CH2) n, where n is an integer from 2 to 6, and CH2CH2OCH2CH 2--, X being halogen of atomic number between 17 and 35 inclusive.

LOUIS H. IBOCK.

Neish, Rectrav. Chim., vol. 66, pp. 433-442 

